English

Extending Nonlocal Kinetic Energy Density Functionals to Isolated Systems via a Density-Functional-Dependent Kernel

Materials Science 2026-03-17 v3 Chemical Physics Computational Physics

Abstract

The Wang-Teter-like nonlocal kinetic energy density functional (KEDF) in the framework of orbital-free density functional theory, while successful in some bulk systems, exhibits a critical Blanc-Cances instability [J. Chem. Phys. 122, 214106 (2005)] when applied to isolated systems, where the total energy becomes unbounded from below. We trace this instability to the use of an ill-defined average charge density, which causes the functional to simultaneously violate the scaling law and the positivity of the Pauli energy. By rigorously constructing a density-functional-dependent kernel, we resolve these pathologies while preserving the formal exactness of the original framework. By systematically benchmarking single-atom systems of 56 elements, we find the resulting KEDF retains computational efficiency while achieving an order-of-magnitude accuracy enhancement over the WT KEDF. In addition, the new KEDF preserves WT's superior accuracy in bulk metals, outperforming the semilocal functionals in both regimes.

Keywords

Cite

@article{arxiv.2507.08442,
  title  = {Extending Nonlocal Kinetic Energy Density Functionals to Isolated Systems via a Density-Functional-Dependent Kernel},
  author = {Liang Sun and Mohan Chen},
  journal= {arXiv preprint arXiv:2507.08442},
  year   = {2026}
}

Comments

7 pages, 6 figures

R2 v1 2026-07-01T03:56:16.592Z